Staudinger ligation of peptides at non-glycyl residues

The Staudinger ligation provides a means to form an amide bond between a phosphinothioester and azide. This reaction holds promise for the ligation of peptides en route to the total chemical synthesis of proteins. (Diphenylphosphino)methanethiol is the most efficacious of known reagents for mediating the Staudinger ligation of peptides, providing high (> 90%) isolated yields for equimolar couplings in which a glycine residue is at the nascent junction. Surprisingly, the yields are lower (< 50%) for non-glycyl couplings due to an aza-Wittig reaction that diverts the reaction toward a phosphonamide byproduct. Here, the partitioning of the reaction toward Staudinger ligation (and away from the aza-Wittig reaction) is shown to increase with increasing electron density on phosphorus. This electron density can be tuned either by installing functional groups on the phenyl substituents of (diphenylphosphino)methanethiol or by changing the polarity of the solvent. Installing p-methoxy groups and using a solvent of low polarity (such as toluene or dioxane) provide especially high (> 80%) isolated yields for the ligation of two non-glycyl residues. These conditions retain the high chemoselectivity of the reaction and do not lead to a substantial change in reaction rate. The traceless Staudinger ligation is now poised to enable the iterative ligation of peptides with little regard for their sequence, as well as the synthesis of amide bonds for other purposes.     

Simultaneous forward- and backward-hemisphere elastic-light-scattering patterns of respirable-size aerosols

Two-dimensional angular optical scattering (TAOS) patterns of aerosols are measured simultaneously from the forward hemisphere 15 degrees < theta < 90 degrees as well as the backward hemisphere 90 degrees < theta < 165 degrees (detecting 63% of the 4pi sr of scattered light) by using an ellipsoidal reflector and an intensified CCD detector. TAOS patterns were obtained from polystyrene-latex spheres (individuals and aggregates) and from single Bacillus subtilis spores. These information-rich patterns, measured with a single laser pulse for individual particles on the fly, suggest that forward-TAOS and backward-TAOS measurements may be used for rapid classification of single aerosol particles.     

Dimethylsilylaminophosphane heterocyclization of isothiocyanates to diazaphosphole‐thiones through zwitterionic intermediates

Isothiocyanates react with Me₂P‐N(SiMe₃)₂ with elimination of (Me₃Si)₂S to give new structurally characterized heterocyclic diazaphosphole derivatives, and in one case the intermediate zwitterionic compound was isolated and structurally characterized. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:196–202, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20595     

The effect of signal duration on the underwater detection thresholds of a harbor porpoise (Phocoena phocoena) for single frequency-modulated tonal signals between 0.25 and 160 kHz

The underwater hearing sensitivity of a young male harbor porpoise for tonal signals of various signal durations was quantified by using a behavioral psychophysical technique. The animal was trained to respond only when it detected an acoustic signal. Fifty percent detection thresholds were obtained for tonal signals (15 frequencies between 0.25-160 kHz, durations 0.5-5000 ms depending on the frequency; 134 frequency-duration combinations in total). Detection thresholds were quantified by varying signal amplitude by the 1-up 1-down staircase method. The hearing thresholds increased when the signal duration fell below the time constant of integration. The time constants, derived from an exponential model of integration [Plomp and Bouman, J. Acoust. Soc. Am. 31, 749-758 (1959)], varied from 629 ms at 2 kHz to 39 ms at 64 kHz. The integration times of the porpoises were similar to those of other mammals including humans, even though the porpoise is a marine mammal and a hearing specialist. The results enable more accurate estimations of the distances at which porpoises can detect short-duration environmental tonal signals. The audiogram thresholds presented by Kastelein et al. [J. Acoust. Soc. Am. 112, 334-344 (2002)], after correction for the frequency bandwidth of the FM signals, are similar to the results of the present study for signals of 1500 ms duration. Harbor porpoise hearing is more sensitive between 2 and 10 kHz, and less sensitive above 10 kHz, than formerly believed.     

A Numerical Study of Blowup in the Harmonic Map Heat Flow Using the MMPDE Moving Mesh Method

The numerical solution of the harmonic heat map flow problems with blowup in finite or infinite time is considered using an adaptive moving mesh method. A properly chosen monitor function is derived so that the moving mesh method can be used to simulate blowup and produce accurate blowup profiles which agree with formal asymptotic analysis. Moreover, the moving mesh method has finite time blowup when the underlying continuous problem does. In situations where the continuous problem has infinite time blowup, the moving mesh method exhibits finite time blowup with a blowup time tending to infinity as the number of mesh points increases. The inadequacy of a uniform mesh solution is clearly demonstrated.     

High electrocatalytic oxidation of folic acid at carbon paste electrode bulk modified with iron nanoparticle-decorated multiwalled carbon nanotubes and its application in food and pharmaceutical analysis

Ionics - A simple and rapid method was employed for the modification of carbon paste electrode with iron nanoparticle-decorated multiwalled carbon nanotubes (MCPE/Fe-MWCNTs). The synergistic effect...     

Characterizing changes in MR images with color-coded Jacobians

Image registration is the process of establishing spatial correspondence between two images or between two image volumes. Registration can be achieved by rigid, elastic, or a combination of rigid and elastic transforms that attempt to bring the two images into coincidence. A rigid transform accounts for differences in positioning and an elastic transform describes deformations due to differences in tissue properties, temporal changes due to growth or atrophy, or differences between individuals. Deformation-based morphometry uses the resulting deformation fields from these transforms to evaluate differences between the images being registered. Three methods of registration were evaluated: rigid (affine) transformation, elastic optical flow transformation, and elastic spline transformation. All three methods produce vector deformation fields that map each point in one image to a point in the other image. A 12-color map of the transformation Jacobian was used to represent local volume changes. Using the three registration methods, color-mapped Jacobians were determined using a simulated three-dimensional block with known translation, rotation, expansion, contraction, and intensity modulations. Color-coded Jacobians were also generated for experimentally measured magnetic resonance image volumes of water-filled balloons and 7-year-old twin boys. Color-coded Jacobians overlaid on anatomical images provide a convenient method to identify regional tissue expansion and contraction.     

The effect of sensorimotor activation on functional connectivity mapping with MRI

The correlations in the fluctuations in the blood oxygenation level-dependent (BOLD) MRI signal between anatomically distinct regions of the cortex that are known components of functional systems have been previously studied as possible indicators of functional connectivity. The objective of this study was to examine the effect of sensorimotor brain activity, as assessed by task-based functional magnetic resonance imaging (fMRI), on functional connectivity indices in the same region. Regions of activation for sequential finger motion were determined using a task-based, block-design fMRI study. Functional connectivity measurements based on interregional correlations were acquired at rest and during continuous, sequential finger motion. Connectivity indices were determined using normalized mean correlations within and between three regions of interest activated for the finger motion task. Connectivity indices were also determined for a control region that was not activated for the task. Continuous motor tasks performed during BOLD measurements did not significantly affect the functional connectivity as compared to the connectivity at rest within or between regions known to be activated by the task. However, there appeared to be a trend suggesting a slight reduction in connectivity indices during the motor task. The connectivity within and between those areas not activated for the task remained unchanged between conditions. These results suggest that in the motor system investigated, the recruitment of neurons to perform a specific task may moderately reduce the degree of hemodynamic coupling within and between regions.     

Spectral Changes Due to Performance Environment in Singers, Nonsingers, and Actors

From postrecording interviews of professional singers, it was hypothesized that recording environments, i.e., sound-treated environment versus an auditorium, may induce different vocal behaviors. To test this hypothesis, three groups consisting of nonsingers, singers, and actors were recorded in two different recording environments: a sound-treated booth (IAC) and an auditorium (AUD). Three recordings were obtained from each participant: recording one (IAC) and two (AUD1) required the participants to read in a normal voice; recording three (AUD2) required participants to pretend that they were "performing" before a full house. Results indicated that only the singers and the actors exhibited significant spectral and/or frequency/duration differences from one recording environment to another, with the most dramatic differences exhibited by the singers. It was concluded that the environment in which we record experimental samples from professional voice users, especially singers, should be considered as a variable that can affect results.